420 



SCIENCE. 



I N. S. Vol. VIII. No. 196. 



and saponified the triester one-third ; they 

 tlieu mixed tlie potassium salt of the re- 

 sulting diester with potassium acetate and 

 subjected the mixture to electrolysis. Large 

 quantities of ethyl succinic ester were 

 formed, a proof of the presence of the un- 

 symmetrical diester in the saponification 

 product, for the symmetrical diester would 

 have yielded methyl glutaric ester. The 

 authors went farther. They had obtained 

 a diester acid, constitution unknown, while 

 preparing the triester. The i)otassium salt 

 of this diester acid they mixed with potas- 

 sium acetate and electrolyzed as before. 

 The product again gave ethyl succinic ester, 

 showing that the original body was the un- 

 symmetrical diester. These are the first 

 examples of electi-osynthesos being used to 

 determine constitution wliich could not bo 

 arrived at in any other way. 



Mullikon has also brought to light a new 

 class of olectrosyntheses. He has directed 

 his investigation mainly to bodies contain- 

 ing a — CH,^ — or — ClI — group, in union 

 with more negative groups. We know that 

 such substances contain hydrogen, which 

 can be replaced by metals. Their sodium 

 salts in alcoholic solution conduct them- 

 selves like electrolytes ; they break down 

 into sodium and a complex anion — the car- 

 bonaceous residue. " The products ob- 

 tained in all the electrosyntheses thus far 

 made are the same one would expect to be 

 formed by the action of iodine on the so- 

 dium or silver compounds of the substances 

 electrolyzed : 



2C,H„0,,Na + 21 = 2NaI-t- CjHjCCOjCjHj),, 

 Sodium Diethyl Malonate Ethyl Ethane-tetracarb- 



o-xylate. 

 2C,HiiOiNa ( electrolyzed ) = 2Na -f- C.HX CO,a Hj ) , . " 



"Weoms has continued this line of investi- 

 gation and from his results has felt justified 

 in concluding that the electrosyntheses 

 effected from malouio ester, methin-tri- 

 carboxylic ester, acetylacetoue and aceto- 

 acetic ester are best explained as the result 



of the direct union of the anions. " Pairing 

 of anions has been shown to be of particu- 

 larly common occurrence in the electrolysis 

 of sodium compounds of derivatives of 

 malonic ether." Such pairing has been 

 observed in certain examples of the aceto- 

 acetic ester type, but it can scarcely be said 

 to be general. Pairing of anions does not 

 take place in the electrolysis of compounds 

 like acetamide, benzamide, succinimide and 

 phthalimide. The same holds with their 

 sodium and mercury salts. 



A very recent synthesis is that of dini- 

 trohexane, a result of the electrolysis of 

 potassium nitroisopropane. 



Lot us take a cursory glance at the de- 

 portment of the alcohols when exposed to 

 the current. Methyl and ethyl alcohol have 

 been elctrolyzed with electrodes of platinum 

 and electrodes of other substances, with and 

 without diaphragms. The results have 

 been of the most varied character. In 

 aqueous sulphuric acid solution methyl 

 alcohol gave methyl formate, acetic acid 

 and methyl acetate. Formic aldehyde was 

 not observed. Methane was produced when 

 the electrolyzed solution contained potas- 

 sium carbonate. Ethyl alcohol, in sul- 

 phuric acid solution, gave acetic acid, formic 

 ester and ethyl sulphuric acid. Chlorinated 

 acetic acids were obtained when hydro- 

 chloric acid was substituted for sulphuric 

 acid. Glycol in sulphuric acid gave trioxy- 

 methylene, gylceric acid, formic acid and an 

 isomeric glucose. Glycerol yielded formic 

 and acetic acids, together with glyceralde- 

 hyde. Chloral hydrate, in presence of sul- 

 phuric acid, with a diaphragmed cell j'ielded 

 chloi-ine and acetaldehyde. The hexa- 

 hydric alcohols and sugars gave products - 

 similar to those obtained from glycerol. 

 Thus, grape sugar was resolved into carbon 

 dioxide, carbon monoxide, trioxymethylene 

 and saccharic acid; 



Now turn with me to the aromatic series. 

 It is hei-e that stable nitro-derivativea 



